Finishing of textile fibers, tissues, and fabrics

ABSTRACT

A method is provided for the application of a finishing layer to a textile support material. A water repellent or oil repellent layer, a so-called finishing layer, is applied to a textile support material selected from the group of fibers, tissues, and fabrics. The water repellent or oil repellent finishing layer comprises at least two water repellent or oil repellent components wherein a first component comprises one or more dispersants and a second component comprises one or more dispersed phases or colloids, and wherein the dispersant and the dispersed phase are present in the gel state. Additionally, textile articles are provided having the novel water repellent or oil repellent finishing layer which are equal on a high level or even superior with respect to their functional properties to products prepared according to known finishing methods and at the same time allow a complete or partial substitution of the health and environmentally hazardous standard chemicals employed nowadays by novel compounds which have not been used to date.

The present invention relates to water and oil repellent textile fibersand fabrics as well as to a method for the finishing of textile fibers,tissues, and fabrics, and particularly to the generation of washing andcleaning resistant, water and oil repellent finishing effects on textilefibers, tissues, and fabrics. These finishing effects are commonlyreferred to a water repellent and oil repellent finishing.

Today, a plurality of water repellent finishing chemicals is used intextile processing which are classified into the wash-resistant and thenot wash-resistant waterproofing agents on the one hand and intofluorocarbon-containing and not fluorocarbon-containing waterproofingagents on the other hand. Another group comprises thesilicone-containing waterproofing agents. The use of silicone-containingwaterproofing agents is also known in combination with fluorocarbonresins. Heavy metal-containing fatty acid derivatives, particularlyparaffins with organometallic compounds, are employed alone and incombination with fluorocarbon resins in the finishing of textile fibers,tissues and fabrics.

Common to all waterproofing agents is their more or less apolar, waterinsoluble character due to which they are used in the form of emulsionsor microemulsions, respectively.

Nowadays, waterproofing agents which are not wash-resistant are of lessimportance since also the quality of the water repellent finishingeffects achieved by them does no longer comply with today's standardsand requirements.

The most widely used products and the finishings produced by them,respectively, are based on reactive, lipid modified αaminoalkylationproducts, fluorocarbon resins, and silicone derivatives or the mixturesthereof. According to present processing technique, best water repellentfinishing effects can only be achieved using fluorocarbon resins or incombination with lipid modified, reactive, pre-polycondensedα-aminoalkylation products (extenders) and self-crosslinking binders(boosters).

Lipid modified, reactive group-containing compounds refers to all thosecompounds which contain at least one reactive group in addition to oneor more covalently bound alkyl groups (C₈-C₂₅). Preferably used lipidmodified α-aminoalkylation products are N-methylol compounds of fattyamines, fatty amides as well as formaldehyde-methylolated ureaderivatives which may also contain partially etherified methylolfunctions.

Due to the growing environmental awareness of the consumers on the onehand and increasingly strict legal regulations on the other hand thereis an increasing demand for textile finishings which meet even thelatest ecological standards. This means that both the fiber materialsused and the colorants and finishing agents must be environmentallyfriendly in the broadest sense. The consumer demands textiles which maybe worn safely. This means in the case of clothing that they should benon-irritant and free from allergenic substances but at the same timefulfill the highest demands for wearing comfort and functionality.

During textile manufacturing it is necessary to ensure the handlingsafety of the starting materials and the finishing and auxiliary agentsused. Also the safe disposal of the waste chemicals, waste, waters, andoutgoing air arising upon production and processing is called for Andeventually, in the sense of a closed system, the textiles should bedisposed of or recycled with an as low environmental pollution aspossible.

Taken together, these demands have already today resulted in anoutlawing of many dyestuffs, halogenated and silicone-containingchemicals as well as the silicones themselves, as used e.g. in the waterrepellent finishings of clothing and technical fabrics. In particular,halogenated finishing agents, if used, result in waste water componentswhich are difficult to dispose of as well as in problems with thedisposal of the technical textiles and clothing finished therewiththemselves after their serviceable life has expired.

It is an object of the present invention to accomplish a novel method oftextile finishing, particularly for water and oil repellent finishing oftextiles (water repellency and oil repellency) which enables thepreparation of textile fibers and fabrics that are equal on a high levelor even superior with respect to their functional properties to productsprepared according to known finishing methods and at the same time allowa complete or partial substitution of the standard chemicals employedtoday by novel compounds which have not been used to date.

It is another object of the present invention to provide water repellentand oil repellent finishings of textiles enabling a complete or at leastpartial regeneration of the water or oil repellent finishing effectwhich abates with time.

It is another object of the present invention to provide a method fortextile finishing enabling the elimination of undesired, environmentallyhazardous chemicals without having to lower one's sights with respect toquality and functionality of the finishing.

These objects have been achieved by a novel water repellent or oilrepellent finishing layer according to claim 1, novel textile articlesaccording to claim 19, and a novel finishing method according to claim23.

An essential feature of the invention is the use of a dispersion system(wherein dispersions also comprises emulsions) as a “guest-host” systemwhich enables a spatial self-organization of the finishing components.By this self-organization of the “guest” and the “host” components, i.e.the dispersed phase and the dispersant, an anisotropic distribution ofthe “guest” component or the dispersed phase within the “host” componentis achieved within the finishing layer. In the final finishing layer,the “guest” component concentrates at the upper surface of the finishinglayer and thereby dominates the physical, chemical, and physico-chemicalproperties at this phase boundary layer between the finishing layerapplied and the surrounding atmosphere.

If gelling additives such as high molecular weight solublepolysaccharides or polar crosslinking components, e.g. glycerol andmethoxy methylolated urea derivatives, are added to the water phase ofthe dispersion system, membrane formation on the tissue occurs inaddition to the above-mentioned self-organization. In the course of thisprocess, the initially homogenous dispersion system partitions dependingon the drying conditions into two liquid phases referred to ascoacervates. One of these predominantly contains the gelling polymerfractions while the other is dominated by the apolar, water or oilrepellent components. Due to the crosslinking reaction that progressesduring the drying process a contraction of the polymer gel occursleading to the formation of the pore system of a membrane out of theoriginally gel-like structure.

The final finishing layer essentially corresponds to a dispersion in thegel state. The heterodisperse system may be utilized for the formationof columnar structures and thereby for the generation on the finishedtextile of a microrough surface exerting the so-called “lotus effect”.This phenomenon is known from nature (Ultrastructure and chemistry ofthe cell wall of the moss Rhadocarpus purpurascens: a puzzlingarchitecture among plants [1, 2]) and is transferred according to thepresent invention to textile water repellent or oil repellentfinishings. The natural “lotus effect” is based on a three-dimensionalsurface structure wherein the wax crystals formed on leafs byself-organization account for a microroughness strongly promoting theself-cleaning effect of the plant [3].

Self-organization and formation of membrane structures, i.e. thetendency to undergo partial phase separation of the “guest” and the“host” components, results in an accumulation of the hydrophobic oroleophobic “guest” components at the surface, i.e. the phase separationlayer between the finishing layer and the surrounding air. Thus,self-organization of the “guest” and “host” components results indramatically enhanced water repellent or oil repellant finishing effectsat the upper surface of the finishing layer as compared to ahomogenously dispersed system.

In contrast to known methods the novel method of finishing permits thecomplete or partial elimination of environmentally hazardous chemicals.The chemicals to be used are selected in each case either due to theproperty profile required from the finishing or with respect to theirphysical, chemical, and physico-chemical suitability with regard to a)the formation of the desired three-dimensional surface structure (thecolumnar structure to achieve the “lotus” effect) and/or b) a inherentphase instability forming of the water repellent or oil repellentfinishing liquor.

According to claim 1, for this purpose at least two differentwaterproofing chemicals as well as crosslinkable, gelatinizing chemicals(dispersant and dispersed phase) are applied to the fiber or tissuesurface which due to their physical, chemical, and physico-chemicalproperties result in the desired microroughness and/or in an inherentphase instability of the water repellent finishing liquor during thesubsequent drying and setting process.

Self-organization and membrane formation are determined by means of thephase instability as well as phase transitions of one or more of thefinishing components.

Thus, essential features of the water repellent finishing system aredifferent physical conditions of the water repellent components and/orthermodynamic instability of the mixed phase (oil in water emulsion) dueto which one of the water repellent components increasingly orientatesat the phase boundary layer (liquid/gas phase or solid/gas phase)similar to a tenside in the context of a self-organization process orfor example leads to the formation of columnar structures. Thedispersion is in the form of a sol during application and is transferredinto the gel state as the procedure proceeds. During this process, oneof the water repellent components, namely the “host” or dispersant,forms an amorphous matrix or membrane structure into which the secondarycomponent, i.e. the “guest” or the dispersed phase, is embedded incorrespondence with a “guest-host” system.

The secondary or “guest” components may be roughly divided into twogroups with respect to their functional properties. There are the“lotus” components on the one hand, and the “micellar” components on theother hand. Both groups of components show a certain mobility duringdrying until they are set which is of high importance for theself-organization and thus for the desired water repellent or oilrepellent finishing effect.

The novel finishing layer permits an at least partially reversibletransfer of the gel state of the dispersant and dispersed phase into thesol state by energy supply. This enables a complete or at least partialregeneration of the abating water repellency or oil repellency,particularly after the finishing layer has been worn down for anextended period. For this purpose it is not necessary to provide anyexternal material. The capability of self-organization and the mobilityof the colloids in the sol-like dispersion lead to a reorganization andconcentration at the surface of the finishing layer, the interface tothe surrounding medium. In the easiest of cases, the water repellent oroil repellent effect of a textile article having the novel finishinglayer may be refreshed already by simple heating in the tumble dryer.

The “guest-host” system described may be extended by additionalcomponents depending on the property profile required from thefinishing. Examples are the co-application of polymeric film formers toboth enhance the adhesion on the textile material and thewash-resistance of the finishing.

Of essential importance for self-organization or formation of columnarstructures, respectively, is the preparation of the water repellent oroil repellent finishing liquors. For this purpose, the major componentwith respect to its quantity (extender) of the water repellent or oilrepellent finishing system is brought into an aqueous emulsion intowhich the secondary component generally being even more apolar than themajor component is emulsified. At the same time, a second solution isprepared containing the gelatinizing chemicals, i.e. the polymericbinder and optional catalysts. An oil in water emulsion is preparedusing the two solutions by emulsifying the emulsion containing thewaterproofing agents into the aqueous solution containing the gellingchemicals. Emulsifying of the water repellent or oil repellent finishingcomponents is effected using e.g. rapidly rotating stirrer (rotor/statorprinciple) or high-pressure mixing systems. The water repellent or oilrepellent finishing liquors prepared in this manner are applied to thetextile material by conventional industrial application techniques suchas padding, coating, spraying or foaming.

For improved adhesion of the water repellent or oil repellent finishinglayer, particularly in the case of synthetic fiber materials, there maybe applied adhesive layers which are also referred to as primer layers.The purpose of forming a primer layer on synthetic tissues is to providedirectly or indirectly polymer attached reactive groups for covalentbinding of the water repellent or oil repellent chemicals and the binderchemicals of the water repellent or oil repellent finishing layer. Inthe case of native fiber materials the function of the primer layersprimarily is regulation of swelling or of the crush resistance which isoften required in addition to water or oil repellency.

The formation of primer layers and the use thereof depend on thechemical nature of the support material. In the case of supportmaterials made of synthetic or regenerated fibers, tissues or fabrics ithas been found advantageous to form the primer layer either directlyfrom a modified support material surface or to apply crosslinked naturalor synthetic hydroxyl, carbonyl, amino, or thiol group containingpolymers onto the support material. For example polyester materialsprovide the possibility to generate polymer bound hydroxyl and carbonylgroups via partial saponification of the polyester. During these partialsaponifications upper layers of the polyester material are removed whichcorrespond to a fraction of 0.01 to 1% of the polyester material,preferably 0.2 to 0.4%.

Reactive groups which are indirectly polymer bound may be formed forexample by application of natural or synthetic hydroxyl group containingpolymers such as lignin, polysaccharides, polyvinyl alcohol etc. andsubsequent crosslinking with e.g. isocyanates or α-aminoalkylationproducts such as dimethylol ethylene urea or hexamethylol melaminederivatives.

The binders or gelatinizing agents used in combination with thewaterproofing agents may be crosslinkable polycondensed formaldehyderesins (Luwipal 66 of BASF company) or the individual componentsthereof, prepolymeric acrylic or methacrylic acid derivatives,isocyanates, polyurethanes etc. in combination with multiple reactivegroup containing compounds such as polysaccharides, glycerol, orgelatin. Each of the binder or gelling systems is characterized bylimited water miscibility, a property which they show inherently orafter an appropriate thermal treatment.

As the major water repellent finishing components, also referred to asextenders, there may be used monomeric or prepolymeric orprepolycondensed but in any case lipid modified apolar acrylates,methacrylates, isocyanates or epoxide and urea derivatives which can beset in the textile material in a wash-resistant manner by thermaltreatment and appropriate catalysts.

Due to its' properties, the “guest” component or dispersed phase ismainly responsible for the self-organization of the water repellent oroil repellent finishing layer (phase separation) and for the formationof columnar structures having a directional orientation at the phaseboundary layer, and may consist of widely different but always veryapolar water or oil repellent auxiliary agents depending on the propertyprofile of the finishing.

-   -   Specifically mentioned may be silicone oils, lipid modified        esters, ethers, or amides (such as glycerol ester and ether,        sorbitan ester and ether) being high boiling point, apolar        liquids which diffuse towards the phase boundary layer        (solid/gas) during the setting process and are set in a position        promoting the water repellent or oil repellent finishing effect.    -   Another group includes fatty esters, alkyl ethers (C₁₂-C₂₅) and        for example polycondensed fatty amides which are dispersed into        the water repellent or oil repellent finishing emulsion in the        form of solids and melt completely or only partially during the        subsequent thermal setting and dominate the interface with their        physical properties in accordance with the desired effect.    -   A third group comprises substances which form columnar        structures. This group includes e.g. micronized waxes (particle        sizes of 0.1-50 μm, preferably around 20 μm) such as polyolefin        and fatty amide waxes as well as waxes being lipid modified        aminoalkylation products, and hydrophobic silica particles        (particle sizes of 5 to 100 nm), preferably nanoparticles having        particle sizes of 5 to 50 nm which are also dispersed into the        water repellent or oil repellent finishing liquor and are        afterwards set in the finishing layer. Examples of such        substances are Ceridust waxes (Clariant) or Aerosils (Degussa)        which are preferably used.

The following Examples are illustrative of the efficiency of the method.

EXAMPLE 1

A primer layer is formed on a polyester tissue having a square meterweight of 180 g by partial saponification (0.3%) for bonding thepolyester to the water repellent layer. The tissue thus pretreated isimpregnated with a water repellent finishing liquor using a liquor ratioof about 60%., then dried and condensed at 150° C. for 3 minutes. Thewater repellent finishing liquor contains the following components:Water 923.5 ml/l Citric acid 5 g/l Aluminium sulfate 0.5 g/l PerapretHVN (binder) 26 g/l Guar gum (gelatinizing 2 g/l agent) Phobotex FTC(extender) 40 g/l Glycerol monooleate 5 g/l

The water repellent tissue is characterized by very good test valueswhich otherwise can only be achieved by fluorocarbon resins or siliconeimpregnations, respectively (see Table 1). Test criteria were the spraytest according to ISO 4920-1981, the water repellency value according toBundesmann (ISO 9865/1993) as well as the percentage of water absorptionduring the rain shower test determined gravimetrically. TABLE 1 Waterrepellency test values after 3 washings (according to EN Initially26330) Spray test 100% 100% Water absorption  9%  12% Water repellency1′/5, 5′/5, 10′/5 1′/5, 5′/4, 10′/4 values

EXAMPLE 2

A primer layer is formed on a polyester tissue having a square meterweight of 250 g by partial saponification (0.5%). The tissue thuspretreated is impregnated on a padding machine using a liquor ratio of55%, and dried continuously on a tenter at 80° C. Setting of the waterrepellent finishing is performed at 160° C. for 3 minutes. Besides theother components the water repellent finishing liquor contains waterrepellent silica nanoparticles (Aerosil R812S) responsible for thecolumnar structures of the water repellent finishing layer. Water 757ml/l Acetic acid 5 g/l Aluminium sulfate 0.5 g/l Glycerol 3 g/l LyofixCHN 9 g/l Cerol EWL 220 g/l Tripalmitin 4 g/l Aerosil R812S 1.5 g/l

In addition to very good water repellency results (Tab. 2) the treatedtissue is characterized by a very soft “dry” handle; this is in contrastto silicone-based water repellent finishings which account for a slickhandle. Another advantage is the improved slip resistance of the tissue.The test criteria are analogous to Example 1. TABLE 2 Water repellencytest values Initially after 3 washings Spray test 100% 100% Waterabsorption  7%  9% Water repellency 1′/5, 5′/5, 10′/5 1′/5, 5′/5, 10′/5values

EXAMPLE 3

Prior to water repellent finishing, a scoured and bleached cotton tissuehaving a square meter weight of 150 g is impregnated with a solutioncontaining a crosslinker to minimize water penetration into the fibersas well as swelling of the fibers upon subsequent contamination withwater. To prepare this primer layer the impregnating liquor contains 10g/l Rucon FAN (Rudolf Chemie), 3 g/l citric acid, 5 g/l magnesiumchloride, and 10 g/l Perapret HVN (BASF). Following impregnation withthe primer liquor, the tissue is dried at 110° C. for two minutes.Subsequently, the water repellent finishing liquor is applied whichcontains all components for generating the water repellent finishingeffect created by phase separation. Water 922.3 ml/l Guar gum 2 g/lCitric acid 3 g/l Aluminium sulfate 1 g/l Phobotex FTC 50 g/lMethacrylic acid dodecylester 15 g/l Urea peroxide 1.5 g/l Iron sulfate0.2 g/l Tris-(trimethylsilyl)-phosphate 5 g/l

After impregnating the tissue on a padding machine (liquor ratio of 72%)drying is performed on a tenter at 100° C. Setting of the waterrepellent chemicals is done also on a tenter at 160° C. for two minutes.The water repellent finishing generated in this manner shows test valuesanalogous to those found for Examples 1 and 2. TABLE 3 Water repellencytest values Initially after 3 washings Spray test 100% 100% Waterrepellency 1′/5, 5′/5, 10′/5 1′/5, 5′/5, 10′/5 values

EXAMPLE 4

A pretreated and dyed cotton/polyester tissue (70/30) having a squaremeter weight of 120 g is impregnated with a crosslinker solution forsubsequent crosslinking of the cotton portion and dried and precondensedat 130° C. The crosslinker is a low-formaldehyde urea derivative(dimethoxy ethylene urea) using citric acid and magnesium chloride ascatalysts.

In a second operation, oil repellent finishing of the tissue is carriedout by applying to the tissue a liquor containing the followingcomponents and drying for one minute at 120° C. The liquor absorption is65% based on the dry weight of the tissue. Water 953 ml/l Acetic acid60% 1 ml/l Ruco-Guard EPF 1561 40 g/l Ruco-Guard LAD 4 g/l Aerosil R812S2 g/l

Setting is performed on a tenter frame at a temperature of 160° C. forone minute.

The finished tissue shows very good water repellency and oil repellencyas apparent from the test values presented in Table 4. TABLE 4 Table ofoil repellency measuring values Initially after 3 washings Spray test100% 100% Water repellency 1′/5, 5′/5, 10′/5 1′/5, 5′/5, 10′/5 valuesOil repellency* 6 6*according to AATCC Test Method 118-1997 (Oil repellency: HydrocarbonResistance Test)

EXAMPLE 5

A two-ply fabric having the following composition: 80% polyami, 10% PESCoolmax®, and 10% Lycra having a square meter weight of 170 g is coatedwith a foamed liquor for water repellent finishing the tissue primarilyon one face. The coating liquor contains all chemicals required forachieving the water repellent finishing effect and for the formation ofcolumnar structures. Water 914.5 g/l Citric acid    5 g/l Aluminiumsulfate  0.5 g/l Phobotex FTC   60 g/l Glycerol    3 g/l Lyofix CHN   10g/l Tripalmitin    4 g/l Ceridust 9615A    3 g/l

The water repellent finishing liquor is dosed into the coating device ofthe tenter frame via a foam forming aggregate and is thus applied ontoone face of the tissue. Drying is performed at a cooling temperaturelimit of about 50° C. on the above-mentioned tenter on which also thesubsequent condensation/setting is carried out. This is performed at160° C. for two minutes.

The effects achieved with this finishing (Tab. 5) demonstrate a verygood water repellent effect with simultaneous good moisture transportwhich is very important for sportswear. TABLE 5 Test values of thefinishing Initially after 3 washings Spray test 100% 100% Waterrepellency 1′/5, 5′/5, 10′/5 1′/4, 5′/4, 10′/4 values Water absorption 7%  13%

EXAMPLE 6

A polyamide tissue having a square meter weight of 150 g is impregnatedwith a liquor the ingredients of which form columnar structures due tothe self-organization of the components occurring during setting.Wollpol A 702 (acidic crosslinking acrylic polymer, Reinhold company),and acrylic stearate are components of the binder system for improvedsetting of Phobotex FTC which is emulsified within the liquor in theform of a microdispersion. Using a padding machine the water repellentfinishing liquor is applied to the tissue which is afterwards dried andcondensed on a tenter. The water repellent finishing liquor consists ofthe following components: Water 825.5 ml/l Isopropanol 50 ml/l Meyproguar gum Casaa 2 g/l M-200 Magnesium chloride × 6H₂O 4 g/l Wollpol A 70250% 30 g/l Acrylic stearate 10 g/l Phobotex FTC 75 g/lAzoisobutyronitrile 0.5 g/l

The drying temperature is 60° C. and the condensation conditions are150° C. and a treatment period of 2.5 minutes.

The water repellent finishing prepared in this manner is characterizedby very good effects as demonstrated in Table 6. The thus waterproofedtissue is excellently suitable for the use in sportswear articles.Initially after 3 washings Spray test 100% 100% Water repellency 1′/5,5′/5, 10′/5 1′/5, 5′/5, 10′/5 values Water absorption  3%  8%

With respect to two further Examples a “host” system on the basis ofacrylate will be described in the following. Substitution of the abovedescribed stearin modified melamine formaldehyde resins by stearinmodified polyacrylate has been found advantageous i.a. for the stabilityof the emulsion. Various modified acrylic and methacrylic acid monomers(for example: acrylic acid dodecyl ester, methacrylic acid dodecylester, acrylic acid and methacrylic acid esters with terminal tertiarybutyl group, acrylic acid and methacrylic acid esters withtrimethylsilane group) were examined resulting in a statically modified,meltable, crosslinkable prepolymer upon emulsion polymerization.

EXAMPLE 7

A polyester tissue having a square meter weight of 230 g is impregnatedwith a water repellent finishing liquor the “host” component of whichconsists of stearyl modified, crosslinkable acrylic polymer. Thepreparation of the acrylic polymer is carried out according to anemulsion polymerization process. The acrylic polymer is used in the formof a 20-40% stock emulsion. For improved stabilization of the“guest-host” system, the triglyceride (“guest”) which migrates on thetissue to the layer surface during setting is admixed already in thepreparation of the acrylate emulsion. The stock emulsion containing theacrylic polymer and the triglyceride is then introduced into a waterprecharge according to the following protocol. The stearyl modifiedacrylic polymer is characterized by very good film formation whichoccurs during drying in a temperature range of 60-90° C. Water  733 g/lIsopropanol   80 g/l Sorbitan monolaurate  2.5 g/l (Span 20) Acrylatestock  180 g/l emulsion 32% Aerosil R 812 S  4.5 g/l

The water repellent finishing liquor is applied by impregnation of thetissue. The liquor weight is 48% based on the dry weight of the tissue.The drying conditions are 100° C. for 1.5 minutes followed bycondensation at 150° C. for 2 minutes.

With respect to the water repellency criteria, the water repellentfinishing prepared on acrylate basis may be directly compared toPhobotex finishings but has the further advantages of substantiallyhigher liquor stability and a virtually formaldehyde-free finishing.Initially after 3 washings Spray test 100% 100% Water absorption  6%  8%Water repellency 1′/5, 5′/5, 10′/5 1′/5, 5′/4, 10′/4 values

EXAMPLE 8

A polyester tissue designed for use in the sportswear article sector isprovided with a water repellent finishing in accordance to the“guest-host” principle already mentioned several times above. The “host”system is formed by an acrylic prepolymer prepared from a monomermixture consisting of methacrylic acid, methacrylic dodecyl ester andtertiary butyl amino ethyl methacrylate (SERPOL QMO 204) according tothe emulsion polymerization procedure. To prepare the acrylate stockemulsion, 10% of a stearyl triglyceride based on the monomer weight isadmixed into the monomer mixture. The solids content of the acrylatestock emulsion is 35%. The acrylic prepolymer containing thetriglyceride has an excellent melting behaviour at 50-90° C. incombination with the desired film formation and the autodynamicorientation of the triglyceride an the layer surface. To prepare thewater repellent finishing liquor, the acrylate stock emulsion is stirredinto a water precharge together with the other partially predispersedchemicals (e.g. Aerosil R 812 S). Water 794 g/l Isopropanol  50 g/lAcrylate stock emulsion 150 g/l 35% Aerosil R 812 S  5 g/lPolyvinylpyrrolidone K  1 g/l 90

Application is performed by impregnation of the tissue using a liquorratio of 55% followed by drying at 110° C. for 1.5 minutes. Subsequentcondensation leads to self-crosslinking of the acrylic polymer resultingin a very high washing resistance.

Tissues finished according to this protocol show very good waterrepellency properties together with high washing resistance whichotherwise can only be achieved using fluorinated waterproofing agents.Initially after 3 washings Spray test 100% 100% Water absorption  5%  7%Water repellency 1′/5, 5′/5, 10′/5 1′/5, 5′/5, 10′/5 values

REFERENCES

-   [1] H. G. Edelmann, C. Neinhuis, M. Jarvis, B. Evans, E. Fischer, W.    Barthlott    -   “Ultrastructure and chemistry of the cell wall of the moss        Rhacocarpus purpurascens: a puzzling architecture among plants”,    -   Planta (1998) 206, 315-321-   [2] PCT/EP95/02934,    -   Priority date: P 44 26 962.5 of Jul. 29, 1994    -   Appicant: W. Barthlott,    -   Title: “Self-cleaning surfaces of objects and process for        producing same”-   [3] W. Barthlott, C. Neinhuis,    -   “Nur was rauh ist, wird von selbst sauber” Technische Rundschau        No. 10 (1999), 56-57

1-18. (canceled)
 19. A textile article comprising textile fibers orfabrics, and a water repellent or oil repellent finishing layer onto asupport material wherein the finishing layer comprises at least twocomponents wherein a first component comprises one or more dispersant(s)and a second component comprises one or more dispersed phase(s), whereinthe dispersed phase comprises at least one colloid and whereindispersant and dispersed phase are present in a gel state and whereinthe colloids of the dispersed phase are distributed in the dispersant inan anisotropic manner such that the colloids are concentrated in thearea of the upper surface of the finishing layer.
 20. The textilearticle according to claim 19 further comprising a primer layer betweenthe support material and the water repellent or oil repellent finishinglayer wherein said primer layer increases adhesion and bonding of thewater repellent or oil repellent finishing layer.
 21. The textilearticle according to claim 20 wherein said textile material comprisesnative materials and said primer layer comprises components which aredeswelling and crosslinking with respect to the textile material. 22.The textile article according to claim 20 wherein said support materialcomprises synthetic and regenerated fibers, tissues, or fabrics, andthat said primer layer is formed by a modified support material surfaceor by crosslinked natural or synthetic hydroxyl, carbonyl, amino, orthiol group containing polymers.
 23. A method for the application of awater repellent or oil repellent finishing layer onto a textile supportmaterial wherein the material is selected from the group consisting offibers, tissues, and fabrics comprising the steps of: applying to thematerial a dispersion comprising one or more dispersant(s) and adispersed phase comprising at least two components wherein the dispersedphase comprises at least one colloid and wherein dispersant anddispersed phase are present in a gel state, and wherein the colloids ofthe dispersed phase are distributed in the dispersant in an anisotropicmanner such that the colloids are concentrated in the area of the uppersurface of the finishing layer; and drying the material, to convert thedispersion from a sol state to a gel state.
 24. The method of finishingaccording to claim 23 wherein said finishing layer is dried to a dryingdegree of almost 5%.
 25. The method of finishing according to claim 23wherein said dispersion is prepared by oil in water (O/W) emulsion of ahydrophobic dispersant in water and subsequent emulsifying of thedispersed phase therein.
 26. The method of finishing according to claim24 wherein the gel state may be transferred in at least partiallyreversible manner into the sol state by energy supply.
 27. The method offinishing according to claim 23 further comprising the step of applyinga primer layer to the material before the application of the finishinglayer, wherein said primer layer improves the adhesion of the waterrepellent or oil repellent finishing layer.
 28. The method of finishingaccording to claim 23 wherein reactive groups are provided for covalentbinding of the water repellent or oil repellent finishing layer to thematerial, wherein said reactive groups are bound to the support materialeither directly or indirectly via the primer layer.
 29. The method offinishing according to claim 27 wherein said support material is acotton material and wherein the primer layer comprises a solutioncomprising a crosslinker solution which is impregnated into the materialto form the primer layer to inhibit the penetration of water into thecotton fibers and thereby minimize fiber swelling.
 30. The method offinishing according to claim 29 wherein said primer layer comprisespartially etherified hexamethylol melamine or dimethylol ethylene ureaderivatives.
 31. The method of finishing according to claim 27 whereinsaid support material is a synthetic or regenerated material selectedfrom the group consisting of fibers, tissues, and fabrics, wherein thesurface of the support material polymer is modified to comprise boundhydroxyl or carbonyl groups.
 32. The method of finishing according toclaim 31 wherein said support material is a polyester material and thesurface is modified by a partial saponification of 0.01 to 1%,preferably a partial saponification of 0.2 to 0.4%.
 33. The method offinishing according to claim 27 wherein said support material is asynthetic or regenerated material selected from the group consisting offibers, tissues, and fabrics, and wherein the primer layer is formed byapplying reactive group containing polymers to the support material andcrosslinking the polymers to form the primer layer wherein hydroxyl,carbonyl, amino and/or thiol groups bound indirectly to the polymer aregenerated on the surface of the support material.
 34. The method offinishing according to claim 33 wherein the reactive group containingpolymers are selected from the group consisting of polysaccharides,lignin, polyvinylalcohol, and the crosslinking is performed by means ofcompounds from the group of isocyanates and α-amylation products. 35.The method of finishing according to claim 27 wherein said dispersioncomprises one or more dispersant(s), a dispersed phase and one or morebinder(s).
 36. The method of finishing according to claim 35 wherein thedispersion to be applied is an emulsion which contains dispersant(s) anddispersed phase emulsified into an aqueous binder containing solution.